Azo dyes of the pyridone series useful for flowable printing inks

ABSTRACT

Azo dyes which in the form of the free bases correspond to the general formula ##STR1## where R 1  is hydrogen, chlorine, bromine, methyl, trifluoromethyl, methoxy, nitro or a radical X, R 2  is hydrogen, chlorine or nitro, R 3  is hydrogen, chlorine, bromine, methyl, methoxy, nitro or a radical X, R 4  is hydrogen or alkyl of 1 to 3 carbon atoms, R 5  is cyano, carbamoyl or acetyl, R 6  is hydrogen, substituted or unsubstituted alkyl or cycloalkyl or a radical X and X is a radical containing an amino group, the molecule containing at least one radical X. The compounds of the formula I are exceptionally useful for improving the flow of pigment-containing printing inks.

SUMMARY OF THE INVENTION

The present invention relates to compounds which in the form of the free bases correspond to the general formula I ##STR2## where R¹ is hydrogen, chlorine, bromine, methyl, trifluoromethyl, methoxy, nitro or a radical X, R² is hydrogen, chlorine or nitro, R³ is hydrogen, chlorine, bromine, methyl, methoxy, nitro or a radical X, R⁴ is hydrogen or alkyl of 1 to 3 carbon atoms, R⁵ is cyano, carbamoyl or acetyl, R⁶ is hydrogen, substituted or unsubstituted alkyl or cycloalkyl or a radical X and X is a radical containing an amino group, and where the molecule contains at least one radical X.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Examples of alkyl R⁴ are propyl, ethyl and especially methyl. Examples of R⁶ are, in addition to hydrogen and the radicals X, alkyl of 1 to 16 carbon atoms (which is unsubstituted or substituted by hydroxyl or alkoxy of 1 to 8 carbon atoms), cyclohexyl, benzyl and phenylethyl. Specific examples are CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, C₆ H₁₃, C₈ H₁₇, C₁₂ H₂₅, C₁₆ H₃₃, CH₂ CH₂ OH, CH₂ CH₂ OCH₃, CH₂ CH₂ OC₄ H₉, (CH₂)₃ OH, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇, (CH₂)₃ OC₄ H₉, ##STR3## (CH₂)₃ OC₈ H₁₇ and CH₂ CHOHCH₃. Preferably, R⁶ is hydrogen, a radical X or CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, ##STR4## C₂ H₄ OCH₃ or C₃ H₆ OC₂ H₅. Examples of radicals X are aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, cycloalkylaminoalkyl and aralkylaminoalkyl, as well as radicals which contain nitrogen as a ring member, and polyaminoalkyl. All these radicals, except R⁶, may also be bonded to the aromatic nucleus via the bridge members --SO₂ NH-- or --CONH--. Alkyl in the radicals X may in addition be substituted, for example by hydroxyl, alkoxy of 1 to 8 carbon atoms or phenoxy, or be interrupted by oxygen.

The radicals X as a rule are of a total of 1 to 18, preferably 3 to 15, and especially 3 to 12, carbon atoms. In polyaminoalkyl, the alkyl chain is interrupted by NH groups; radicals which contain nitrogen as a ring member are preferably saturated.

Specific examples of radicals X are CH₂ NH₂, CH₂ NHCH₃, CH₂ NHC₂ H₅, CH₂ NHC₅ H₁₃, CH₂ NHC₈ H₁₇, ##STR5## CH₂ NHC₁₃ H₂₇, CH₂ N(CH₃)₂, CH₂ N(C₂ H₅)₂, CH₂ N(C₃ H₇)₂, CH₂ N(C₄ H₉)₂, CH₂ N(C₅ H₁₁)₂, CH₂ N(C₆ H₁₃)₂, CH₂ N(C₇ H₁₅)₂, CH₂ N(C₈ H₁₇)₂, CH₂ N(C₂ H₄ OCH₃)₂, CH₂ N(C₂ H₄ OC₂ H₅)₂, CH₂ N(C₂ H₄ OC₃ H₇)₂, ##STR6## CH₂ N(CH₂ CH₂ OH)₂, C₂ H₄ NH₂, C₂ H₄ NHCH₃, C₂ H₄ NHC₂ H₅, C₂ H₄ NHC₃ H₇, C₂ H₄ N(CH₃)₂, C₂ H₄ N(C₂ H₅)₂, C₂ H₄ N(C₄ H₉)₂ C₂ H₄ N(C₅ H₁₀)₂, C₃ H₆ NH₂, C₃ H₆ NHCH₃, C₃ H₆ NHC₂ H₅, ##STR7## C₃ H₆ N(CH₃)₂, C₃ H₆ N(C₂ H₅)₂, C₃ H₆ N(C₃ H₇)₂, C₃ H₆ N(C₄ H₉)₂, C₄ H₈ N(CH₃)₂, C₄ H₈ N(C₂ H₅)₂, C₄ H₈ N(C₃ H₇)₂, CH₂ NH-C₂ H₄ -NH₂, CH₂ NHC₂ H₄ N(CH₃)₂, CH₂ NHC₃ H₆ NHCH₃, CH₂ NHC₃ H₆ N(CH₃)₂, CH₂ NHC₃ H₆ N(C₂ H₅)₂, CH₂ NHC₄ H₈ N(CH₃)₂, CH₂ NHC₄ H₈ N(C₂ H₅)₂, ##STR8## CH₂ NHC₂ H₄ NHC₂ H₄ NH₂, CH₂ NHC₃ H₆ NHC₃ H₆ NH₂, CH₂ NHC₃ H₆ OC₄ H₈ OC₃ H₆ NH₂, C₂ H₄ NHC₃ H₆ NH₂, C₃ H₆ NHC₃ H₆ NH₂, C₃ H₆ NHC₂ H₄ NHC₃ H₆ NH₂, C₃ H₆ NHC₃ H₆ NHC₃ H₆ NH₂, C₃ H₆ NHC₃ H₆ NHC₃ H₆ NHC₃ H₆ NH₂, SO₂ NHC₂ H₄ NH₂, SO₂ NHC₂ H₄ N(CH₃)₂, SO₂ NHC₂ H₄ N(C₂ H₅)₂, SO₂ NHC₃ H₆ NHCH₃, SO₂ NHC₃ H₆ N(CH₃)₂, SO₂ NHC₃ H₆ N(C₂ H₅)₂, SO₂ NHC₃ H₆ N(C₃ H₇)₂, SO₂ NHC₃ H.sub. 6 N(C₄ H₉)₂, SO₂ NHC₄ H₈ NHCH₃, SO₂ NHC₄ H₈ NHC₂ H₅, SO₂ NHC₄ H₈ N(CH₃)₂, SO₂ NHC₄ H₈ N(C₂ H₅)₂, ##STR9## CO₂ NHC₂ H₄ NH₂, CO₂ NHC₂ H₄ N(CH₃)₂, CO₂ NHC₂ H₄ N(C₂ H₅)₂, CO₂ NHC₃ H₆ NHCH₃, CO₂ NHC₃ H₆ N (CH₃)₂, CO₂ NHC₃ H₆ N(C₂ H₅)₂, CO₂ NHC₃ H₆ N(C₃ H₇)₂, CO₂ NHC₃ H₆ N(C₄ H₉)₂, CO₂ NHC₄ H₈ NHCH₃, CO₂ NHC₄ H₈ NHC₂ H₅, CO₂ NHC₄ H₈ N(CH₃)₂, CO₂ NHC₄ H₈ N(C₂ H₅)₂, ##STR10##

Examples of preferred radicals X are CH₂ N(CH₃)₂, CH₂ N(C₂ H₅)₂, CH₂ N(C₃ H₇)₂, CH₂ N(C₄ H₉)₂, CH₂ N(C₅ H₁₁)₂, CH₂ N(C₂ H₄ OCH₃)₂, C₂ H₄ N(CH₃)₂, C₂ H₄ N(C₂ H₅)₂, C₂ H₄ N(C₄ H₉)₂, C₃ H₇ NHCH₃, ##STR11## C₃ H₇ N(CH₃)₂, C₃ H₇ N(C₂ H₅)₂, C₃ H₇ N(C₃ H₇)₂, C₃ H₇ N(C₄ H₉)₂, C₄ H₉ N(C₂ H₅)₂, CH₂ NHC₂ H₄ N(CH₃)₂, CH₂ NHC₃ H₇ N(CH₃)₂, CH₂ NHC₃ H₇ N(C₂ H₅)₂, CH₂ NHC₄ H₉ N(C₂ H₅)₂, ##STR12## SO₂ NHC₂ H₄ N(CH₃)₂, SO₂ NHC₂ H₄ N(C₂ H₅)₂, SO₂ NHC₃ H₆ N(CH₃)₂, SO₂ NHC₃ H₆ N(C₂ H₅)₂, SO₂ NHC₃ H₆ N(C₄ H₉)₂, SO₂ NHC₄ H₈ N(C₂ H₅)₂ SO₂ NHC₄ H₈ N(CH₃)₂, ##STR13## CO₂ NHC₂ H₄ N(CH₃)₂, CO₂ NHC₂ H₄ N(C₂ H₅)₂, CO₂ NHC₃ H₆ N(CH₃)₂, CO₂ NHC₃ H₆ N(C₂ H₅)₂, CO₂ NHC₃ H₆ N(C₄ H₉)₂ CO₂ NHC₄ H₈ N(C₂ H₅)₂, CO₂ NHC₄ H₈ N(CH₃)₂, ##STR14## C₃ H₆ NHC₂ H₄ NHC₃ H₆ NH₂, C₃ H₆ NHC₃ H₆ NHC₃ H₆ NH₂ and C₃ H₆ NHC₃ H₆ NHC₃ H₆ NHC₃ H₆ NH₂.

The compounds of the formual I can be manufactured by coupling a diazonium compound of an amine of the formula II ##STR15## with a compound of the formula III ##STR16##

The diazotization and coupling take place without unusual features; details can be found in the Examples, where parts and percentages are by weight, unless stated otherwise.

The radicals X are present in the individual components of the formula II and/or III. As a rule, they are introduced into the radicals R¹ and R³ by means of halogen compounds, whilst they are introduced into R⁶ during the preparation of the pyridones, in accordance with conventional methods. Some typical methods are described in the Examples.

The compounds of the formula I are exceptionally useful for improving the flow of pigments, to which they are as a rule added, for this purpose, in amounts of from 0.5 to 10%. They may be used in the form of the free bases or of salts, the salts being preferred in some cases. Suitable salts are, in particular, those with organic anions, preferably longchain alkylsulfonates or arylsulfonates. Specific examples of sulfonic acids from which these anions are derived are methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, octanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid, tridecanesulfonic acid, hexadecanesulfonic acid, octadecanesulfonic acid, benzenesulfonic acid, α- and β-naphthalenesulfonic acid, o- and p-toluenesulfonic acid, xylenesulfonic acid, p-tert.-butylbenzenesulfonic acid, o-hydroxy-tert.-butylbenzenesulfonic acid, p-hexylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid octadecylbenzenesulfonic acid, o-hydroxy-m,m'-bis-dodecylbenzenesulfonic acid, o-hydroxynonylbenzenesulfonic acid, o-hydroxydodecylbenzenesulfonic acid, hydroxy-hexadecylbenzenesulfonic acid, hydroxyoctadecylbenzenesulfonic acid, monoalkylnaphtholsulfonic acids and dialkylnaphtholsulfonic acids where alkyl is of 1 to 20 carbon atoms, 1-alkene-1-sulfonic acids of 8 to 20 carbon atoms and 2-hydroxy-alkane-1-sulfonic acids of 8 to 20 carbon atoms.

Compounds of particular industrial importance are those of the formula Ia ##STR17## where A¹ is hydrogen, chlorine, bromine or nitro, A² is hydrogen, alkyl of 1 to 12 carbon atoms, cyclohexyl, benzyl or a radical X and X has the above meaning.

In the phenyl ring, the radical X is preferably in the p-position; preferably, the compounds of the formula I contain one radical X. General method for the manufacture of a compound of the formula II or III

Method A

151 parts of p-cyanobenzyl chloride are introduced into 200 parts of diethylamine and the mixture is refluxed for 2 hours. The excess amine is distilled off, the residue is dissolved in 300 parts of water and 250 parts of isobutanol and the solution is heated with 85 parts of hydroxylammonium sulfate, in the presence of 58 parts of technical-grade sodium carbonate and 10 parts of the sodium salt of diethylenetriaminopentaacetic acid for 5 hours. The mixture is allowed to cool to 50°, 150 parts of isatoic anhydride are introduced and the pH is then brought to 11 with 50 percent strength sodium hydroxide solution. The isobutanol is distilled off quantitatively by introducing steam; the mixture is then cooled to 10° C. and the solid is filtered off, washed with water and dried. 280 parts of the compound of the formula ##STR18## are obtained. The crude material melts at 62° C. whilst material recrystallized from alcohol/water melts at 69° C.

Method B

201 parts of 4-cyanobenzenesulfonic acid chloride are introduced slowly into 130 parts of diethylaminopropylamine, during which time the temperature rises to 60° C. The viscous reaction mixture is dissolved in 250 parts of isobutanol and 300 parts of water, and thereafter the procedure described for Method A is followed. After completion of the reaction, the mixture is neutralized with hydrochloric acid and the product is filtered off and dried. 292 parts of the compound of the formula ##STR19## are obtained; its melting point is 102° C.

Method C

165 parts of m-cyanobenzoyl chloride are introduced dropwise, whilst cooling, into 260 parts of diethylaminopropylamine and the mixture is stirred for 3 hours at room temperature. 300 parts of isobutanol are then added and the organic phase is washed twice with 200 parts of water. The isobutanol phase is then reacted further with hydroxylammonium sulfate, water and sodium carbonate, as described for Method A. 310 parts of the compounds having the structure ##STR20## are isolated. After recrystallization from ethanol/water, the melting point is 160° C.

Method D

260 parts of diethylaminopropylamine are added dropwise to 226 parts of ethyl cyanoacetate in 300 parts of methanol at 35° C. and the mixture is then stirred for 2 hours at the same temperature; thereafter, 170 parts of piperidine and 260 parts of ethyl acetoacetate are added slowly and the mixture is refluxed for 12 hours. All the volatile constituents are then distilled off under reduced pressure. The residue crystallizes on standing in a refrigerator. 520 parts of the compound of the formula ##STR21## are isolated; the melting point is 175° C.

The diazo components referred to in the Examples which follow can be synthesized in accordance with the same principles.

EXAMPLE 1

35 parts of the amine of the formula ##STR22## are stirred with 40 parts of concentrated hydrochloric acid and 150 parts of water for 30 minutes at 60° C. The mixture is then cooled to 0° C. with ice and diazotized by adding 30 parts by volume of a 23 percent strength NaNO₂ solution. After 3 hours, the excess nitrite is destroyed with amidosulfonic acid and a solution of 15 parts of dihydroxycyanomethylpyridine in a mixture of 400 parts of water and 60 parts of 2N sodium hydroxide solution is added slowly to the diazonium salt solution. The pH is brought to 6 with 2N sodium hydroxide solution, the mixture is stirred for 30 minutes and then brought to 60° C. by passage of steam, and 33 parts of dodecylbenzenesulfonic acid in 100 parts of water are added. The product is then filtered off and washed with water. 83 parts of the dye of the formula ##STR23## are obtained.

EXAMPLE 2

43 parts of the amine of the formula ##STR24## are dissolved in 80 parts of dimethylformamide and added dropwise to a well-stirred mixture of 200 parts of water, 500 parts of ice, 70 parts of glacial acetic acid and 48 parts of concentrated hydrochloric acid. The amine is then diazotized by adding 30 parts by volume of NaNO₂ and after about 3 hours excess nitrite is destroyed with amidosulfonic acid.

15 parts of dihydroxycyanomethylpyridone, dissolved in a mixture of 300 parts of water and 60 parts of 2N sodium hydroxide solution, are added dropwise. The pH is then brought to 7 with 5N sodium hydroxide solution, the mixture is heated to 80° C. with steam and 33 parts of dodecylbenzenesulfonic acid in 100 parts of water are added. 88 parts of the dye of the formula ##STR25## are obtained.

Using the method described in Example 2, yellow dyes are obtained from the diazo components and coupling components shown in the Table which follows.

    __________________________________________________________________________        Diazo                         Coupling            Salt formed               Ex.                                                                               component                     component           with                      __________________________________________________________________________         ##STR26##                                                                                                    ##STR27##          hexadecylbenzene-                                                              sulfonic acid             4    "                                                                                                           ##STR28##          dodecylbenzene-                                                                sulfonic acid             5    "                                                                                                           ##STR29##            --                      6                                                                                  ##STR30##                                                                                                    ##STR31##          dodecylbenzene-                                                                sulfonic acid             7    "                             "                 hexadecylbenzene-                                                              sulfonic acid             8    "                                                                                                           ##STR32##          dodecanesulfonic                                                               acid                      9                                                                                  ##STR33##                                                                                                    ##STR34##          dodecylbenzene-                                                                sulfonic acid             10   "                             "                 diisobutyl-                                                                    naphthale-                                                                     sulfonic acid             11   "                                                                                                           ##STR35##          diisobutyl- naphthale                                                          ne- sulfonic acid         12    "                                                                                                          ##STR36##            --                      13                                                                                 ##STR37##                                                                                                    ##STR38##          nonylbenzene-                                                                  sulfonic acid             14   "                                                                                                           ##STR39##          dodecylbenzene-                                                                sulfonic acid             15   "                                                                                                           ##STR40##          octanesulfonic-                                                                acid                      16                                                                                 ##STR41##                                                                                                    ##STR42##          dodecylbenzene-                                                                sulfonic acid             17   "                                                                                                           ##STR43##          dodecylbenzene-                                                                sulfonic acid             18                                                                                 ##STR44##                                                                                                    ##STR45##          dodecylbenzene-                                                                sulfonic acid             19   "                             "                 alkylhexylnaphtha-                                                             sulfonic acid             20   "                                                                                                           ##STR46##          dodecylbenzene-                                                                sulfonic acid             21   "                                                                                                           ##STR47##            --                      22   "                                                                                                           ##STR48##            --                      23                                                                                 ##STR49##                                                                                                    ##STR50##          dodecylbenzene-                                                                sulfonic acid             24                                                                                 ##STR51##                      "                 dodecylbenzene-                                                                sulfonic acid             25                                                                                 ##STR52##                      "                 dodecylbenzene-                                                                sulfonic acid             26                                                                                 ##STR53##                      "                 dodecylbenzene-                                                                sulfonic acid             27                                                                                 ##STR54##                      "                 dodecylbenzene-                                                                sulfonic acid             28                                                                                 ##STR55##                      "                 o-hydroxynonyl-                                                                benzenesulfonic                                                                acid                      29                                                                                 ##STR56##                      "                 dodecylbenzene-                                                                sulfonic acid             30                                                                                 ##STR57##                      "                 dodecylbenzene-                                                                sulfonic acid             31                                                                                 ##STR58##                      "                 p-tert.-butyl-                                                                 phenolsulfonic acid       32   "                             "                   --                      33   "                             "                 ethylhexyl-                                                                    naphthalene-1-                                                                 sulfonic acid             34   "                                                                                                           ##STR59##          dodecylbenzene-                                                                sulfonic acid             35   "                                                                                                           ##STR60##          dodecylbenzene-                                                                sulfonic acid             36   "                                                                                                           ##STR61##          dodecylbenzene-                                                                sulfonic acid             37   "                             "                 dodecylbenzene-                                                                sulfonic acid             38   "                             "                 2 moles of                                                                     dodecylbenzene-                                                                sulfonic acid             39                                                                                 ##STR62##                                                                                                    ##STR63##          dodecylbenzene-                                                                sulfonic acid             40                                                                                 ##STR64##                      "                 dodecylbenzene-                                                                sulfonic acid             41                                                                                 ##STR65##                      "                 dodecylbenzene-                                                                sulfonic acid             42                                                                                 ##STR66##                      "                 dodecylbenzene-                                                                sulfonic acid             43                                                                                 ##STR67##                      "                 dodecylbenzene                                                                 sulfonic acid             44                                                                                 ##STR68##                      "                 dodecylbenzene-                                                                sulfonic acid             45                                                                                 ##STR69##                      "                 dodecylbenzene-                                                                sulfonic acid             46                                                                                 ##STR70##                      "                 dodecylbenzene                                                                 sulfonic acid             47                                                                                 ##STR71##                      "                 dodecylbenzene-                                                                sulfonic acid             48   "                                                                                                           ##STR72##          dodecylbenzene-                                                                sulfonic acid             49   "                                                                                                           ##STR73##            --                      50                                                                                 ##STR74##                      "                 dodecylbenzene-                                                                sulfonic acid             51                                                                                 ##STR75##                      "                 dodecylbenzene-                                                                sulfonic acid             52                                                                                 ##STR76##                      "                 dodecylbenzene-                                                                sulfonic acid             53                                                                                 ##STR77##                      "                 dodecylbenzene-                                                                sulfonic acid             54                                                                                 ##STR78##                      "                 dodecylbenzene-                                                                sulfonic acid             55                                                                                 ##STR79##                                                                                                    ##STR80##            --                      56                                                                                 ##STR81##                                                                                                    ##STR82##          dodecylbenzene-                                                                sulfonic acid             57                                                                                 ##STR83##                      "                 docedylbenzene-                                                                sulfonic acid             58                                                                                 ##STR84##                      "                 dodecylbenzene-                                                                sulfonic acid             59                                                                                 ##STR85##                      "                 dodecylbenzene-                                                                sulfonic acid             60                                                                                 ##STR86##                      "                 dodecylbenzene-                                                                sulfonic acid             61                                                                                 ##STR87##                     10 "               dodecylbenzene-                                                                sulfonic acid             62                                                                                 ##STR88##                      "                 dodecylbenzene-                                                                sulfonic acid             63                                                                                 ##STR89##                      "                 dodecylbenzene-                                                                sulfonic acid             64                                                                                 ##STR90##                      "                 dodecylbenzene-                                                                sulfonic acid             65                                                                                 ##STR91##                                                                                                    ##STR92##            --                      66                                                                                 ##STR93##                                                                                                    ##STR94##          dodecylbenzene-                                                                sulfonic acid             67                                                                                 ##STR95##                      "                 dodecylbenzene-                                                                sulfonic acid             68                                                                                 ##STR96##                      "                 dodecylbenzene-                                                                sulfonic acid             69                                                                                 ##STR97##                      "                 dodecylbenzene-                                                                sulfonic acid             70                                                                                 ##STR98##                      "                 dodecylbenzene-                                                                sulfonic acid             71                                                                                 ##STR99##                      "                 dodecylbenzene-                                                                sulfonic acid             72                                                                                 ##STR100##                                                                                                   ##STR101##         dodecylbenzene-                                                                sulfonic acid             73                                                                                 ##STR102##                                                                                                   ##STR103##         dodecylbenzene-                                                                sulfonic acid             74   "                             "                 dodecylbenzene-                                                                sulfonic acid             75                                                                                 ##STR104##                     "                 dodecylbenzene-                                                                sulfonic acid             76                                                                                 ##STR105##                     "                 dodecylbenzene-                                                                sulfonic acid             77                                                                                 ##STR106##                     "                 dodecylbenzene-                                                                sulfonic acid             78   "                             "  --                                       79                                                                                 ##STR107##                                                                                                   ##STR108##         dodecylbenzene-                                                                sulfonic acid             80                                                                                 ##STR109##                                                                                                   ##STR110##         dodecylbenzene-                                                                sulfonic acid             81                                                                                 ##STR111##                     "                 dodecylbenzene-                                                                sulfonic acid             82                                                                                 ##STR112##                     "                 dodecylbenzene-                                                                sulfonic acid             83                                                                                 ##STR113##                     "                 dodecylbenzene-                                                                sulfonic acid             84                                                                                 ##STR114##                     "                 dodecylbenzene-                                                                sulfonic acid             85                                                                                 ##STR115##                     "                 dodecylbenzene-                                                                sulfonic acid             86                                                                                 ##STR116##                                                                                                   ##STR117##         dodecylbenzene-                                                                sulfonic acid             87   "                                                                                                           ##STR118##           --                      88   "                                                                                                           ##STR119##           --                      89   "                                                                                                           ##STR120##           --                      90   "                                                                                                           ##STR121##         dodecylbenzene-                                                                sulfonic acid             91   "                                                                                                           ##STR122##           --                      92                                                                                 ##STR123##                     "                   --                      93   "                                                                                                           ##STR124##           --                      94                                                                                 ##STR125##                     "                 dodecylbenzene-                                                                sulfonic acid             95                                                                                 ##STR126##                     "                 dodecylbenzene-                                                                sulfonic acid             96                                                                                 ##STR127##                                                                                                   ##STR128##         dodecylbenzene-                                                                sulfonic acid             97                                                                                 ##STR129##                     "                 dodecylbenzene-                                                                sulfonic acid             98                                                                                 ##STR130##                     "                 dodecylbenzene-                                                                sulfonic acid             99                                                                                 ##STR131##                     "                 dodecylbenzene-                                                                sulfonic                  __________________________________________________________________________                                                          acid                 

USE EXAMPLE

10 parts of the dye of the formula ##STR132## and 0.4 part of the dye obtained as described in Example 1 are mixed thoroughly, in a dispersing apparatus, with from 30 to 40 parts of a resin (eg. a rosin-modified phenol-formaldehyde resin) and from 55 to 65 parts of toluene. This gives a toluene gravure ink which has great tinctorial strength and brilliance, and excellent flow. 

What is claimed as new and intended to be covered by Letters Patent is:
 1. A compound useful for improving the flowability of pigment-containing printing inks which in the form of the free base corresponds to the formula ##STR133## where R¹ is hydrogen, chlorine, bromine, methyl, trifluoromethyl, methoxy, nitro or X,R² is hydrogen, chlorine or nitro, R³ is hydrogen, chlorine, bromine, methyl, methoxy, nitro or X, R⁴ is hydrogen or alkyl of 1 to 3 carbon atoms, R⁵ is cyano, carbamoyl or acetyl, R⁶ is hydrogen, C₁ to C₁₆ alkyl, C₂ to C₈ alkyl substituted by hydroxy or C₁ to C₈ alkoxy, cyclohexyl, benzyl, phenylethyl and ##STR134## m is 1, 2, 3 or 4 n is 2, 3, or 4 p is 0, 1, 2 or 3 Y is a direct bond, --CONH-- or --SO₂ NH--, B¹ is hydrogen, C₁ to C₁₃ alkyl or C₂ or C₃ alkyl substituted by hydroxy or C₁ to C₈ alkoxy, B² is hydrogen, C₁ to C₈ alkyl; C₂ or C₃ alkyl substituted by hydroxy or C₁ to C₈ alkoxy; or cyclohexyl and B¹ and B² together with the nitrogen are pyrrolidino, piperidino, methylpiperidino, morpholino, piperazino, N-methylpiperazino or N-β-hydroxyethylpiperazino with the proviso that the molecule contains at least one group X.
 2. A compound according to claim 1 in whichR¹ is hydrogen, chlorine, methyl or nitro, R² hydrogen, chlorine or nitro, R³ is hydrogen, chlorine, bromine, methyl or X, R⁴ is hydrogen or methyl, R⁵ is cyano, R⁶ is hydrogen C₁ to C₈ alkyl, C₂ or C₃ alkyl substituted by hydroxy or C₁ to C₄ alkoxy; and X has the meaning given for claim
 1. 3. A compound according to claim 1 in whichR¹ and R² are hydrogen, R³ is X, R⁴ is methyl, R⁵ is cyano, R⁶ is hydrogen, C₁ to C₄ alkyl and X has the given meaning.
 4. A compound according to claim 1 in whichR¹, R² and R⁶ are hydrogen, R³ is X, R⁴ is methyl, R⁵ is cyano and X has the given meaning.
 5. A compound according to claim 3 in which ##STR135## B³ is C₁ to C₈ alkyl, B⁴ is C₁ to C₈ alkyl,B³ and B⁴ together with the nitrogen are pyrrolidino, piperidino, morpholino, piperazino or N-methylpiperazino and m, n, p and R¹ to R⁶ have the given meanings.
 6. A compound according to claim 4 in whichR³ is X and ##STR136## R¹, R², R⁴, R⁵, R⁶, B¹ and B² having the given meanings.
 7. The compound according to claim 1 of the formula ##STR137##
 8. A method for improving the flowability of pigment containing printing inks, which comprises adding to said printing ink a compound which in the form of the free base corresponds to the formula ##STR138## where R¹ is hydrogen, chlorine, bromine, methyl, trifluoromethyl, methoxy, nitro or X,R² is hydrogen, chlorine or nitro, R³ is hydrogen, chlorine, bromine, methyl, methoxy, nitro or X, R⁴ is hydrogen or alkyl of 1 to 3 carbon atoms, R⁵ is cyano, carbamoyl or acetyl, R⁶ is hydrogen, C₁ to C₁₆ alkyl, C₂ to C₈ alkyl substituted by hydroxy or C₁ to C₈ alkoxy, cyclohexyl, benzyl, phenylethyl and ##STR139## m is 1, 2, 3, or 4 n is 2, 3 or 4 p is 0, 1, 2 or 3 Y is a direct bond, --CONH-- or --SO₂ NH--, B¹ is hydrogen, C₁ to C₁₃ alkyl or C₂ or C₃ alkyl substituted by hydroxy or C₁ to C₈ alkoxy, B² is hydrogen, C₁ to C₈ alkyl; C₂ or C₃ alkyl substituted by hydroxy or C₁ to C₈ alkoxy; or cyclohexyl and B¹ and B² together with the nitrogen are pyrrolidino, piperidino, methylpiperidino, morpholino, piperazino, N-methylpiperazino or N-β-hydroxyethylpiperazino with the proviso that the molecule contains at least one group X.
 9. The method of claim 8 wherein said printing ink has the formula ##STR140##
 10. A printing ink which comprises a pigment of the formula ##STR141## and an amount of an additive sufficient to improve the flowability of said pigment, of the formula ##STR142## where R¹ is hydrogen, chlorine, bromine, methyl, trifluoromethyl, methoxy, nitro or X,R² is hydrogen, chlorine or nitro, R³ is hydrogen chlorine, bromine, methyl, methoxy, nitro or X, R⁴ is hydrogen or alkyl of 1 to 3 carbon atoms, R⁵ is cyano, carbamoyl or acetyl, R⁶ is hydrogen, C₁ to C₁₆ alkyl, C₂ to C₈ alkyl substituted by hydroxy or C₁ to C₈ alkoxy, cyclohexyl, benzyl, phenylethyl and ##STR143## m is 1, 2, 3 or 4 n is 2, 3 or 4 p is 0, 1, 2 or 3 Y is a direct bond, --CONH-- or --SO₂ NH--, B¹ is hydrogen, C₁ to C₁₃ alkyl or C₂ or C₃ alkyl substituted by hydroxy or C₁ to C₈ alkoxy. B² is hydrogen, C₁ to C₈ alkyl; C₂ or C₃ alkyl substituted by hydroxy or C₁ to C₈ alkoxy; or cyclohexyl and B¹ and B² together with the nitrogen are pyrrolidino, piperidino, methylpiperidino, morpholino, piperazino, N-methylpiperazino or N-β-hydroxyethylpiperazino with the proviso that the molecule contains at least one group X. 